CN101466751A - Method for the production of (meth)acrylate-based ABA triblock copolymers - Google Patents
Method for the production of (meth)acrylate-based ABA triblock copolymers Download PDFInfo
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- CN101466751A CN101466751A CNA2007800215105A CN200780021510A CN101466751A CN 101466751 A CN101466751 A CN 101466751A CN A2007800215105 A CNA2007800215105 A CN A2007800215105A CN 200780021510 A CN200780021510 A CN 200780021510A CN 101466751 A CN101466751 A CN 101466751A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
Abstract
The invention relates to a method for producing (meth)acrylate-based ABA triblock copolymers in which the A blocks are amine-functionalized.
Description
Technical field
The present invention relates to a kind of preparation based on (methyl) acrylate and wherein the A block by the method for amine-functionalized ABA triblock copolymer with relate to it for example as the purposes of the preparaton composition of reactive adhesive or sealing agent.
Background technology
Multipolymer with customization (ma β geschneidert) of specific composition, chain length, molar mass distribution etc. is wide research field.Be divided into gradient polymer and block polymer especially.Can consider different purposes for these materials.Wherein some of following brief introduction.For this reason, the Application Areas of Xuan Zeing especially, the polymkeric substance that wherein uses the present invention to demarcate with it.
The Application Areas of polymkeric substance of the present invention is as the reactive preparaton composition in the tackiness agent.This class tackiness agent for example is described among the US 5,021,507.Main component is the compound with free isocyanate groups group, and these compounds mainly obtain by the excessive polyisocyanates group and the condensation reaction of polyvalent alcohol.For improving the adhesive property on the specific base material, in having the compound of free isocyanate groups group, these add binding agent, and described binding agent is made up of the polymkeric substance that ethylenically unsaturated monomer forms.Typically use as binding agent and to have C
1To C
20Poly-(methyl) alkyl acrylate of alkyl group.They are by obtaining by free Raolical polymerizable polymerization before corresponding monomer is in adding carbamate to or in the presence of it.
As the replacement scheme of employed polyvalent alcohol, also can consider to use amine-functionalized poly-(methyl) acrylate.Amine groups has obviously higher reactivity than oh group at isocyanic ester.Possibility by selecting functionality to be regulated cross-linked speed pointedly thus.Draw the preparaton that wherein has the functional binding agent with hydroxyl-functional of amine simultaneously, and to make preparaton in this way be the useful possibility that progressively is solidified into from machining angle for paying close attention to ining addition.
At US 5,866,656 and EP 1036103 in reactive hot-melt adhesive has been described, wherein, the binding agent that is made of poly-(methyl) acrylate covalently is bonded on the compound that has free isocyanate groups group in the binder composition.Because this bonding is mainly undertaken by condensation reaction, so this tackiness agent that wherein forms this bonding is called tackiness agent in the condensation stage.So the tackiness agent that obtains is than US 5,021, and those described in 507 are characterised in that the elasticity of raising and have better adhesivity on the special metal base material and in the longer time that is used to process of opening wide.
Usually be known that, except with the reaction of isocyanic ester, two kinds of application of main consideration amine functional group are (for this reason referring to B.M ü ller in tackiness agent and sealing agent field, W.Rath, Formulierungen von Kleb-und Dichtstoffen, the 1st edition, Vincentz, the Hanover, 2004): primary amine and secondary amine at first are used as the stiffening agent of Resins, epoxy.In this way, improving the polymerization degree can realize with the amine of simple function.Adopt polyfunctional construction package (Baustein) can carry out crosslinking reaction.Containing functionalized poly-(methyl) acrylate is very novel adhesive formulation prescription as the bicomponent system of reactive component.On the other hand, the ring-opening polymerization of tertiary amine catalytic epoxide.Also can consider two component adhesive material preparaton based on this prescription.But different with above-mentioned preparaton, in this case, amine component in shortage is also enough.
Secondly, can use primary diamines with dicarboxylic acid or secondary diamine with the structure polymeric amide.Equally can be polyfunctional by using, high poly--or oligomeric component with these known polycondensations for a long time as the curing mechanism that is used for adhesive formulation or sealant formulations.
The shortcoming of the adhesive formulation of prior art is the higher viscosity of work in-process.Obviously make the processing (at first promptly being the coating on porous substrate) of jointing material become difficult thus.In some cases, also can in the condensation stage gelation appear.
In addition disadvantageously, but also contain the more high-load low molecular composition of crosslinking reaction and the extraction component of corresponding reactive hot-melt adhesive of not participating in through the material of radical polymerization.
The shortcoming that has again is, and is quite high in the tackiness agent of the content that can extract after curing.This has reduced the solvent resistance of jointing material especially.
Closer step with the polyreaction of another kind of type and to go a step further to the target of the polymkeric substance of customization.ATRP-method (atom transition free radical polymerization reaction) is researched and developed (Matyjaszewski etc., J.Am.Chem.Soc., 1995,117,5614 pages by Prof.Matyjaszewski fatefully in generation nineteen ninety; WO97/18247; Science, 1996,272,866 pages), particularly also adopt (methyl) vinylformic acid (dimethylamino) ethyl ester (DMAEMA) (Zhang, Matyjaszewski, Macromolecules; 1999,32, the 1763-1766 page or leaf).Put down in writing purified long DMAEMA block in the segmented copolymer at this piece document.Other description of the monomeric copolyreaction of amino-contained group is arranged in US 6541580 B1 or WO 03/031481 A3.
It is M that ATRP provides the molar mass scope
n=10,000-120, (all) polymkeric substance of the narrow distribution of 000g/mol.At this, a special advantage is that not only molecular weight but also molecular weight distribution all can be regulated.As living polymerization, it has also given the particular configuration of polymer architecture, for example statistical copolymer or block copolymer structure.Can obtain for example unconventional segmented copolymer and star polymer extraly by corresponding initiator.The theoretical basis of polymerization reaction mechanism is especially at Hans Georg Elias, Makromolek ü le, and the 1st volume, the 6th edition, Weinheim1999 obtains explaining in 344 pages.
The transformation that has jumping between the monomer of block polymer in polymer chain, this transformation are the boundaries between each block.The conventional synthetic method of AB-block polymer is the controlled fusion reaction of monomer A and adds monomers B in the follow-up moment.Except adding the sequential polymerisation reactions in the reaction vessel to by batch, when adding these two kinds of monomers continuously,, also can obtain similar result at certain their composition of flip-flop particular moment.
Except negatively charged ion or GROUP TRANSFER POLYMERIZATION, the modernism of controlled radical polymerization also is suitable as living polymerisation process or controlled fusion method, for example RAFT-polyreaction.The mechanism of RAFT-polyreaction is further described among WO 98/01478 or the EP 0910587.Put down in writing Application Example among the EP 1205492.
Problem mentioned above is so solved in WO 05/047359, promptly by using controlled polymerisation process (with the form of atom transfer radical polymerization), binding agent with very narrow molecular weight distribution can be provided, it is characterized in that (methyl) acrylate with respect to radical polymerization only has a small amount of macromolecule component content.Described composition causes the rising of viscosity especially in polymeric blends.
But, be in the polymer chain of binding agent the statistical distribution of oh group, mercapto groups or amine groups according to the shortcoming of the prepared reactive adhesive of WO05/047359.This has caused close net crosslinked (engmaschige Vernetzung) and has therefore caused the elasticity of jointing material to reduce.Also may cause base material bonding variation thus.Have when surpassing polyisocyanates that two free isocyanate groups roll into a ball as the preparaton composition of reactive hot-melt adhesive when using especially, this shortcoming just becomes burden.Being used for enumerating and describing the compound with free isocyanate groups group can describe accordingly with reference to WO05/047359.
Second case description of the potential use of this polymkeric substance with gradient-structure or block structure is in hereinafter:
For with solid in the liquid or solid medium, homodisperse in paint vehicle, aqueous pigment dispersion or the moulding material (all thermoset in this way and thermoplastic polymer) for example, and randomly that it is stable adds dispersion agent as auxiliary agent.For this reason, they must have different character, for example interact with surface of pigments.In addition, dispersion agent should have in molecule and the good compatible zone of medium.For organic medium, for example be hydrophobic structure, as aryl structure or alkyl structure.For water-bearing media, should use water miscible hydrophilic-structure, for example polyoxyethylene glycol.
Usually use polymkeric substance (as (methyl) acrylate or vinylbenzene) based on ethylenically unsaturated monomer as dispersion agent.Monomer is usually by the radical polymerization action-reaction.Can only in chain, obtain statistical monomer distribution with traditional method.But, can only be very poor with the effective dispersive possibility of this polymer architecture.Also can only resist very limitedly and form the foamy problem.Therefore, need the new polymers structure for the optimization when using described mode.
For forming seldom foamy dispersion liquid, the segmental gradient copolymer that in for example DE 10236133 and DE 1416019, has unusual polar, constitutes by hydroxyl-functional or the functional repeating unit of amine by living polymerization or controlled fusion prepared in reaction.Gradient copolymer is the multipolymer of for example being made up of monomer A and B, in its single chain, exists the distribution gradient of monomer structure assembly along chain.An end of the chain is rich in monomer A and lacks monomers B, and the other end then is rich in monomers B and lacks monomer A.The difference of gradient copolymer and segmented copolymer is that smooth transition is arranged between monomer A and the B.
Amine-functionalized segmented copolymer by means of ATRP preparation mainly has description in the use as dispersion agent: describe the A-B Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and have at least 50% the amine-functionalized degree of A block in WO 00/40630.This invention and difference of the present invention are that segmented copolymer is one-sided end-functionalized, longer block, high functionalized degree and the higher generally manufacturing cost of polymkeric substance thus.In WO 03/046029 A1, be described in further detail corresponding building-up process, and at first described and have dispersing of pigments liquid.But, the more favourable Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of relative triblock copolymer for dispersion has also just been described here.EP 1501881 A1 equally also are so, and it has described Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock amine-functionalized in one or two block and its terminal group functional that is undertaken by substitution reaction subsequently.
In Auschra etc., described the amine-functionalized block with homopolymerization the A-B-Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock (Progress in Organic Coatings, 2002,45,83-93).The preparation of the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock with amine-functionalized homopolymer block has been described in WO02/28913A2 similarly.Amine groups is transformed into quaternary ammonium group subsequently in similar polymeric reaction (polymeranalogeReaktion).But this approach just directly synthesizes the alternative of ionic polymer in Aquo System in WO 02/28913, also is described among the US2006/0008490 A1 as it.(J.Polym.Sci.-A part: Polym.Chem. in Gan etc., 2003,41,2688-2695), similar this amine functional blocks ground combines with methacrylic tert-butyl acrylate block, so that the saponification by the subsequently and block that the potential anionic acid is functionalized combines with potential ammonium cation block.
Chatterjee etc. (Polymer, 2005,46,10699-10708) the ABA triblock copolymer with amine-functionalized outer block has been described.But different with the present invention, described block is the homopolymerization block, and it makes in order to realize extra high polarity.Yet this is not a purpose of the present invention.At this more is to be devoted to introduce less functional activity group.Invention of being quoted and difference of the present invention also be, for the polymkeric substance described in this specification sheets, not being desirably in has big solvability difference and in fact this is deleterious between the block.
Another purposes of amine-functionalized block is a cosmetic applications, for example hair flushing.The ABA triblock copolymer of the polysiloxane B-block that has amine-functionalized A-block and introduce as macromole evocating agent has in advance been described in EP1189976 B1 or EP 1189975 A1.At this, purpose also is subsequently amine groups to be changed in the ammonium cation group.With other differences of the present invention be the building-up processes in three steps to four steps altogether of polymkeric substance and the solvability with respect to pure poly-(methyl) acrylate difference of polysiloxane segment.Same application is based on JP 2004277300 A2.But, amine groups is described just as the surrogate of methacrylic acid potassium block at this, bring and the adhesivity of using relevant protein surface by it.
Other purposes are particularly as the purposes of consistency promotor in the polymeric blends, as the prepolymer that makes up the polymer block structure, as the binding agent of tackiness agent or as the purposes of the binding agent of sealing material.
A new developmental stage is the triblock copolymer of the following stated, is divided into ABC and ABA-triblock copolymer.
The ABA-triblock copolymer also is equal to the 5-segmented copolymer that consists of ACBCA.
Summary of the invention
Task of the present invention is to prepare the triblock polymer of ABA structure.Particularly exist to end capped (methyl) acrylate of amine or its aspect of performance corresponding to or very near the demand of (methyl) acrylate of the end capped material of amine.This can for example realize by embed one or several amine groups at the end of the chain.The end of the chain is meant polymkeric substance end segment, and it accounts for the highest 1-20 weight % of total polymer weight.
Having amine terminated (methyl) acrylate or amine end capped (methyl) acrylate is suitable as prepolymer and is used for crosslinked, by the use in polycondensation or polyaddition reaction, to be that purpose is carried out further terminated and reacted and construct various block structures in conjunction with the functional group that is difficult for so far tapping into, perhaps be applicable to special biological respinse.
Another task of the present invention is so to provide the polymkeric substance that contains the reactive amine group as binding agent, promptly makes the number of this class group in the polymkeric substance when having good operability for curing reaction, keeps the least possible.Can the causing possible gelation more at high proportion or cause the extra raising of reactive hot-melt adhesive melt viscosity at least of binding agent Semi-polarity group.This task can be by solving in conjunction with functional group near the end of the chain or its targetedly.
Another task is, provides to have this narrow as far as possible, as to be lower than 1.8 molecular weight distribution class material.In this way, no matter be the content that helps to improve undesirably the higher molecular weight component of melt viscosity especially, can cause that still the content of the low-molecular-weight especially composition of jointing material solvent resistance deterioration all can minimize.
Consider clear and definite and the prior art of being discussed, task of the present invention is particularly in providing a kind of reactive adhesive, and described tackiness agent has very big initial intensity and premature gelation can not occur.In addition, can be implemented under the predetermined processing temperature, the viscosity of the melt of reactive adhesive reduces or stable viscosity, thereby has realized the improvement of workability.In addition, but these tasks relate in particular to through the extracted component that has only little content in the solidified jointing material and for many differing materials very good adhesion property.
Therefore, task of the present invention is particularly in providing a kind of binding agent that is used for reactive hot-melt adhesive, and promptly it is that amine is end capped or have a free amine of very few number near the end of the chain.When being mixed with the reactive bonding agent material, this class material has higher jointing material elasticity.Improve the better adhesivity on base material thus.This class polymkeric substance of the present invention also can be used for sealing material.
Described task is passed through to be provided consists of ABA and have in each A-block≤and the segmented copolymer of 4 functional groups solves, it is characterized in that, block A is the monomeric multipolymer that contains amine-functionalized (methyl) acrylate and be selected from (methyl) acrylate or its mixture, and B block contains (methyl) acrylate or its mixture with amine functional group, and block A and B block polymerization are become the ABA-segmented copolymer.
Term (methyl) acrylate is not only represented methacrylic ester at this, and for example methyl methacrylate, Jia Jibingxisuanyizhi etc. are also represented acrylate, for example methyl acrylate, ethyl propenoate etc., and the two mixture.
Find, also can make in each A-block and have≤the ABA-segmented copolymer of 2 amine groups.
Can be both to the multipolymer of block A also in the multipolymer of B block, be added into 0-50 weight % can polymeric and do not belong to the monomer of (methyl) esters of acrylic acid by ATRP.
Preferred embodiment be in ABA forms, to have in each A-block≤segmented copolymer of 4 amine groups, and wherein, block A contains amine-functionalized (methyl) acrylate and is selected from the monomer of (methyl) acrylate or its mixture and randomly other do not belong to the multipolymer of (methyl) acrylic ester monomer by ATRP is polymerisable, B block contains and does not have functional (methyl) acrylate of amine or their mixture and randomly other are polymerisable and do not belong to (methyl) acrylic ester monomer by ATRP, above-mentioned two kinds of block polymerizations are become the ABA-segmented copolymer, wherein, by the polymerisable monomer of ATRP also can be copolymerization go into the A block or just copolymerization go into the B block.
The segmented copolymer that consists of ABA by less than gross weight 20%, preferably constitute less than 10% A-block.
ABA-three blocks also are equivalent to the 5-segmented copolymer that consists of ACBCA.Wherein, the feature of segmented copolymer is, the composition of C-block corresponding in the A-block without the composition of amine-functionalized part.
In a particularly preferred embodiment, the feature of segmented copolymer is that each A-block itself can have AC-diblock structure again and therefore produce five segmented copolymers of ACBCA.
These segmented copolymers can have following feature, the composition of C-block corresponding in the A-block without the composition of amine-functionalized part.
Block A is made of maximum 4 amine-functionalized monomers, and described monomer is made up of amine-functionalized (methyl) esters of acrylic acid.B block does not contain amine-functionalized (methyl) acrylate.
Also researched and developed the preparation method of the segmented copolymer of a kind of ABA of consisting of in addition.Adopt the special shape of living polymerization, (atom transition free radical polymerization reaction (ATRP)) can be embedded into composition, structure and the specific functionality of well-controlled in the polymkeric substance.
Find, adopt dual functional initiator can make up ABA or ACBCA structure pointedly.
Amine-functionalized (methyl) acrylate that polymerization is gone among the block A preferably has general formula H
2C=CR
1-C (=O) XR
2NR
3R
4(methyl) propenoic acid dialkyl aminoalkyl ester, (methyl) acrylic acid alkyl aminoalkyl ester or (methyl) acrylic-amino alkyl ester.Wherein, R
1Be hydrogen or methyl.R
2Expression straight chain, branch or the functionalized hydrocarbon fragment with 2 to 36 C-atoms of alicyclic two-fold, it can be introduced by the esterification of amino alcohol and acrylic or methacrylic acid.X be oxygen or-NH-.R
3And R
4Can refer to identical or also can be different organic residues, described organic residue be selected from straight chain, branch or alicyclic alkyl residue and/or the aromatic yl residue with 2 to 20 C atoms.Particularly preferably be 2-dimethyl aminoethyl-methacrylic ester (DMAEMA), 2-diethylamino ethyl-methacrylic ester (DEAEMA), 2-tertiary butyl amino-ethyl-methacrylic ester (t-BAEMA), 2-dimethyl aminoethyl-acrylate (DMAEA), 2-diethylamino ethyl-acrylate (DEAEA), 2-tertiary butyl amino-ethyl-acrylate (t-BAEA), 3-dimethylaminopropyl-Methacrylamide (DMAPMA) and 3-dimethylaminopropyl-acrylamide (DMAPA).
The monomer that not only polymerization is gone among the block A but also polymerization is gone in the B block is selected from (methyl) esters of acrylic acid, for example, straight chain with 1 to 40 C atom, (methyl) alkyl acrylate of branch or alicyclic alcohol, for example (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) 2-EHA, (methyl) vinylformic acid octadecane alcohol ester, (methyl) lauryl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate; (methyl) vinylformic acid aryl ester is (methyl) benzyl acrylate or (methyl) phenyl acrylate for example, and they can have respectively and are unsubstituted or 1-4 refetches the aromatic yl residue in generation; (methyl) acrylate that other aromatics replace is (methyl) vinylformic acid naphthalene ester for example; Ether with 5-80 C atom, polyoxyethylene glycol, the list of polypropylene glycol or its mixture (methyl) acrylate, for example tetrahydrofurfuryl methacrylate, methacrylic acid methoxy Ji Jia (second) oxygen base ethyl ester, methacrylic acid 1-butoxy propyl ester, methacrylic acid cyclohexyloxy methyl esters, methacrylic acid benzyloxy methyl esters, methacrylic acid chaff ester, methacrylic acid 2-butoxy ethyl ester, methacrylic acid 2-ethoxy ethyl ester, methacrylic acid allyloxy methyl ester, methacrylic acid 1-oxyethyl group butyl ester, methacrylic acid 1-ethoxy ethyl ester, methacrylic acid oxyethyl group methyl esters, poly-(ethylene glycol) methyl ether (methyl) acrylate and poly-(propylene glycol) methyl ether (methyl) acrylate.
Except aforesaid (methyl) acrylate, treat that the polymeric composition can also contain other unsaturated monomers, described monomer and aforesaid (methyl) but acrylate is copolymerization by means of ATRP.The particularly 1-alkene that belongs to this type of, as the 1-hexene, the 1-heptene, the alkene of branching, vinyl cyclohexane for example, 3,3-dimethyl-1-propylene, 3-methyl isophthalic acid-diisobutylene, 4-methyl-1-pentene, vinyl cyanide, vinyl ester is vinyl acetate for example, vinylbenzene, the vinylbenzene that is substituted that on vinyl, has alkyl substituent, for example alpha-methyl styrene and α-ethyl styrene have the vinylbenzene that is substituted such as the Vinyl toluene and the p-methylstyrene of one or more alkyl substituents on the ring, halogenated styrenes is monochloro-benzene ethene for example, dichlorobenzene ethene, tribromo-benzene ethene and phenyl tetrabromide ethene; Heterogeneous ring compound such as 2-vinyl pyridine, 3-vinyl pyridine, 2-methyl-5-vinylpyrine, 3-ethyl-4-vinylpridine, 2,3-dimethyl-5-vinyl pyridine, vinyl pyrimidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 2-methyl isophthalic acid-vinyl imidazole, vinyl tetrahydrofuran (Vinloxolan), vinyl furans, vinyl thiophene, vinyl tetramethylene sulfide (Vinylthiolan), vinylthiazole, Yi Xi Ji oxazole and prenyl ether; Maleic acid derivatives, maleic anhydride, maleimide, methyl maleimide and diolefine Vinylstyrene for example for example, and in the A-block, each hydroxy-functional and/or aminofunctional and/or hydrosulphonyl functionalized compound.In addition, these multipolymers also can prepare like this, even they have hydroxy functional group and/or amido functional group and/or mercapto functional group in substituting group.These monomers are for example vinyl piperidines, 1-vinyl imidazole, N-vinyl pyrrolidone, 2-vinyl pyrrolidone, N-ethenyl pyrrolidone, 3-ethenyl pyrrolidone, N-caprolactam, N-vinyl butyrate lactam, hydrogenant vinylthiazole and hydrogenant Yi Xi Ji oxazole.Especially preferably make vinyl ester, vinyl ether, fumarate, maleic acid ester, vinylbenzene or vinyl cyanide and A-block and/or B-block copolymerization.
Described method can be carried out in the solvent of Halogen arbitrarily.Preferably toluene, dimethylbenzene, H
2O; Acetic ester, preferably butylacetate, vinyl acetic monomer, propyl acetate; Ketone, preferred methylethylketone, acetone; Ether; Alkane, preferred pentane, hexane, but also can be biofuel.
The segmented copolymer that consists of ABA makes by means of sequential polymerization.
Except solution polymerization, also can carry out ATRP with the form of emulsion, tiny emulsion, microemulsion, suspension or bulk polymerization.
Described polyreaction can be carried out at normal pressure, negative pressure or excessive rolling.Polymeric reaction temperature is not important.But this temperature usually in-20 ℃ to 200 ℃ scope, preferably 0 ℃ to 130 ℃ and particularly preferably in 50 ℃ to 120 ℃ scope in.
Preferred polymkeric substance of the present invention has between 5000g/mol and 100000g/mol, especially preferred≤50000g/mol and extremely preferred number-average molecular weight between 7500g/mol to 25000g/mol.
Find that molecular weight distribution is lower than 1.8, preferably be lower than 1.6, especially preferably be lower than 1.4 and be lower than 1.3 ideally.
Can adopt RO as bifunctional initiator
2C-CHX-(CH
2)
n-CHX-CO
2R, RO
2CC (CH
3) X-(CH
2)
n-C (CH
3) X-CO
2R, RO
2C-CX
2-(CH
2)
n-CX
2-CO
2R, RC (O)-CHX (CH
2)
n-CHX-C (O) R, RC (O)-C (CH
3) X-(CH
2)
n-C (CH)
3X-C (O) R, RC (O)-CX
2-(CH
2)
n-CX
2-C (O) R, XCH
2-CO
2-(CH
2)
n-OC (O) CH
2X, CH
3CHX-CO
2-(CH
2)
nOC (O) CHXCH
3, (CH
3)
2CX-CO
2-(CH
2)
n-OC (O) CX (CH
3)
2, X
2CH-CO
2-(CH
2)
nOC (O) CHX
2, CH
3CX
2-CO
2-(CH
2)
n-OC (O) CX
2CH
3, XCH
2C (O) C (O) CH
2X, CH
3CHXC (O) C (O) CHXCH
3, XC (CH
3)
2C (O) C (O) CX (CH
3)
2, X
2CHC (O) C (O) CHX
2, CH
3CX
2C (O) C (O) CX
2CH
3, XCH
2-C (O)-CH
2X, CH
3-CHX-C (O)-CHX-CH
3, CX (CH
3)
2-C (O)-CX (CH
3)
2, X
2CH-C (O)-CHX
2, C
6H
5-CHX-(CH
2)
n-CHX-C
6H
5, C
6H
5-CX
2-(CH
2)
n-CX
2-C
6H
5, C
6H
5-CX
2-(CH
2)
n-CX
2-C
6H
5, adjacent-,-or right-XCH
2-Ph-CH
2X, adjacent-,-or right-CH
3CHX-Ph-CHXCH
3, adjacent-,-or right-(CH
3)
2CX-Ph-CX (CH
3)
2, adjacent-,-or right-CH
3CX
2-Ph-CX
2CH
3, adjacent-,-or right-X
2CH-Ph-CHX
2, adjacent-,-or right-XCH
2-CO
2-Ph-OC (O) CH
2X, adjacent-,-or right-CH
3CHX-CO
2-Ph-OC (O) CHXCH
3, adjacent-,-or right-(CH
3)
2CX-CO
2-Ph-OC (O) CX (CH
3)
2, CH
3CX
2-CO
2-Ph-OC (O) CX
2CH
3, adjacent-,-or right-X
2CH-CO
2-Ph-OC (O) CHX
2Or adjacent-,-or right-XSO
2-Ph-SO
2(X represents chlorine, bromine or iodine to X; Ph represents phenylene (C
6H
4); R represents by 1 to 20 aliphatic residue that carbon atom constitutes, it can be straight chain, branching or cyclic structure, can be saturated or single or multiple undersaturated and can contain one or more aromatics or not contain aromatics and n be 0 to 20 numeral).Preferred use 1,4-butyleneglycol-two-(2 bromo 2 methyl propionic acid ester), 1-two (2 bromo 2 methyl propionic acid ester), 2,5-two bromo-diethylene adipates or 2,3-two bromo-toxilic acid diethyl ester.If all monomer reactions, then monomeric ratio is drawn subsequently molecular weight by initiator.
The catalyzer of ATRP is described in Chem.Rev.2001, in 101,2921.It has mainly described copper complex, but also especially use iron, rhodium, platinum, ruthenium or nickel compound.Usually, can use all transistion metal compounds that can form oxidation reduction cycle with initiator or the polymer chain with transferable atomic group.For this reason, can be from Cu
2O, CuBr, CuCl, CuI, CuN
3, CuSCN, CuCN, CuNO
2, CuNO
3, CuBF
4, Cu (CH
3COO) or Cu (CF
3COO) set out copper is incorporated in the system.
As the replacement scheme of described ATRP is a kind of identical variation scheme: in so-called reverse ATRP, the compound that can use high oxidation state more is CuBr for example
2, CuCl
2, CuO, CrCl
3, Fe
2O
3Or FeBr
3In these situations, can form for example AIBN initiation reaction of agent by means of traditional free radical.At this, at first transistion metal compound is reduced, because them and the free radical reaction that is formed the agent generation by traditional free radical.Reverse ATRP is recorded in Macromolekules (1995) by Wang and Matyjaszewski especially, and 28 volumes are in the content that 7572 pages are risen.
A variation scheme of reverse ATRP is that to use oxidation state extraly be zero metal.By increasing the acceleration of the speed that induces reaction with the proportioning of the transistion metal compound of high oxidation state (Komproportionierung) more.This method more at large is described among the WO98/40415.
Transition metal, preferably in 0.02:1 to 6:1 and the scope particularly preferably in 0.2:1 to 4:1, but should not limit usually in the scope of 0.02:1 to 20:1 thus to some extent to the molar ratio of bifunctional initiator.
Also avoid forming stable and organometallic compound that have polymerization activity therefrom simultaneously for the solubleness that improves metal in the organic solvent, in system, add ligand.Ligand is also convenient extraly to shift transferable atomic group by transistion metal compound.For example being set forth among WO97/18247, WO97/47661 or the WO98/40415 of known ligand.As the coordinate composition, the compound that is used as ligand in most cases has one or more nitrogen-atoms, phosphorus atom and/or sulphur atom.At this, particularly preferably be nitrogenous compound.Extremely preferably nitrogenous chelating ligand.That describe as an example is 2,2 '-two pyridines, N, N, N ', N "; N "-five methyl diethylentriamine (PMDETA), three (2-amino-ethyl) amine (TREN), N, N, N ', N '-tetramethylethylened or 1,1,4,7,10,10-hexamethyl Triethylenetetramine (TETA).Can in WO98/40415, find for the selection of each composition and valuable prompting those skilled in the art of combination.
These ligands metallizing thing in situ form coordination compound or they and can at first make coordination compound and join in the reaction mixture subsequently.
Ligand (L) depends on the coordination valence of ligand and the ligancy of transition metal (M) with the ratio of transition metal.Usually, molar ratio in the scope of preferred 6:1 to 0.1:1 and preferred especially 3:1 to 1:1, but should not limit in the scope of 100:1 to 0.1:1 thus to some extent.
Another advantage of segmented copolymer is the colourless property and the tasteless property of obtained product.Colourless property is particularly because the preparation method of sulfur-bearing not.
Produce the purposes widely of these products thus.The selection of Application Example is not suitable for limiting the application of polymkeric substance of the present invention.These embodiment should just be used for the wide in range use possibility of the sampling formula ground described polymkeric substance of explanation.The segmented copolymer that preferably will consist of ABA is used for jointing material, sealing material or reactive hot melt adhesive as prepolymer.Described prepolymer can with any crosslinked polymer.Also can consider as binding agent, reactive component or dispersion agent in the paint vehicle preparaton.
Below provide embodiment and be used for illustrating better the present invention, and be not suitable for limiting the invention to feature disclosed herein.
Embodiment
Embodiment
Embodiment 1
In a double-jacket container that is equipped with agitator, thermometer, reflux exchanger, nitrogen conduit and dropping funnel, at N
2Preset monomer 1a (accurately the explanation of title and consumption is in table 1), 115g N-BUTYL ACETATE, 1.15g cupric oxide (I) and 2.9g N under the atmosphere, N, N ', N ", N " five methyl diethylentriamine (PMDETA).Solution was stirred 15 minutes down at 60 ℃.Drip the initiator 1 that is dissolved in the N-BUTYL ACETATE subsequently under uniform temp, 4-butyleneglycol-two (2 bromo 2 methyl propionic acid ester) is (consumption is referring to table 1) (BDBIB).After 3 hours polymerization time, extraction is used for determining molecular-weight average M
nThe sample of (by means of SEC) also adds the mixture of being made up of monomer 2a and monomer 3a (accurately the explanation of title and consumption is in table 1).This mixture of polymerization interrupts reaction until at least 98% transformation efficiency of expection and by being exposed to atmospheric oxygen and randomly adding methylene dichloride.By through the filtration of silica gel and remove volatile component this solution of purifying by distillation subsequently.Measure by SEC subsequently and determine molecular-weight average.The content of the monomer 3a that embeds passes through
1The H-NMR-method of masurement is quantitative.
Embodiment 2
Be similar to embodiment 1, use monomer 1b, 2b and 3b (accurately the explanation of title and consumption is in table 1).
Embodiment 3
Be similar to embodiment 1, use monomer 1c, 2c and 3c (accurately the explanation of title and consumption is in table 1).
Embodiment 4
Be similar to embodiment 1, use monomer 1d, 2d and 3d (accurately the explanation of title and consumption is in table 1).
Table 1
| Embodiment | 1 | 2 | 3 | 4 |
| Monomer 1 | 1a)n-BA | 1b)n-BA | 1c)MMA | 1d)MMA |
| Consumption | 70g | 70g | 70g | 70g |
| Monomer 2 | 2a)MMA | 2b)n-BA | 2c)n-BA | 2d)MMA |
| Consumption | 10g | 10g | 10g | 10g |
| Monomer 3 | 3a)DMAEMA | 3b)DMAEMA | 3c)DMAEMA | 3d)DMAEMA |
| Consumption | 5.5g | 5.5g | 5.5g | 5.5g |
| Initiator amount | 3.2g | 3.2g | 3.2g | 3.2g |
| M n(fs) | 12200 | 12100 | 11100 | 11900 |
| M n(end product) | 17000 | 16200 | 15800 | 15600 |
| D | 1.19 | 1.31 | 1.24 | 1.23 |
The MMA=methyl methacrylate; The n-BA=n-butyl acrylate, DEMEMA=methacrylic acid 2-dimethylamino ethyl ester
Embodiment 5
In a double-jacket container that is equipped with agitator, thermometer, reflux exchanger, nitrogen conduit and dropping funnel, at N
2Preset monomer I a (accurately the explanation of title and consumption is in table 2), 120g N-BUTYL ACETATE, 1.15g cupric oxide (I) and 2.9g PMDETA under the atmosphere.Solution was stirred 15 minutes down at 60 ℃.Drip the initiator 1 that is dissolved in the N-BUTYL ACETATE subsequently under uniform temp, 4-butyleneglycol-two (2 bromo 2 methyl propionic acid ester) (BDBIB).After 3 hours polymerization time, extraction is used for determining molecular-weight average M
nThe sample of (by means of SEC) also adds monomer II a (accurately the explanation of title and consumption is in table 2).After calculating reaches 98% transformation efficiency, add the mixture of forming by monomer II a ' and monomer II Ia (accurately title and consumption illustrate in table 2) at last.This mixture of polymerization interrupts reaction until at least 98% transformation efficiency of expection and by being exposed to atmospheric oxygen and randomly adding methylene dichloride.By through the filtration of silica gel and remove volatile component this solution of purifying by distillation subsequently.Measure by SEC subsequently and determine molecular-weight average.The content of the monomer II Ia that embeds passes through
1The H-NMR-method of masurement is quantitative.
Table 2
| Embodiment | 5 |
| Monomer I | Ia)n-BA |
| Consumption | 40g |
| Monomer II | IIa)MMA |
| Consumption | 40g |
| Monomer II ' | IIa′)MMA |
| Consumption | 10g |
| Monomer II I | IIIa)DMAEMA |
| Consumption | 5.5g |
| Amount of initiator | 3.3g |
| M n(fs) | 11500 |
| M n(end product) | 18400 |
| D | 1.29 |
The MMA=methyl methacrylate; The n-BA=n-butyl acrylate, DMAEMA=methacrylic acid 2-dimethyl aminoethyl ester
Embodiment 6 (comparative example 1)
Synthesizing of the ABA-triblock copolymer of not functionalized
General rule by means of the synthetic described ABA-triblock copolymer of ATRP is:
In a double-jacket container that is equipped with agitator, thermometer, reflux exchanger, nitrogen conduit and dropping funnel, at N
2Preset monomer V1a (accurately the explanation of title and consumption is in table 3), N-BUTYL ACETATE, cupric oxide (I) and PMDETA under the atmosphere.Solution was stirred 15 minutes down at 60 ℃.Drip the initiator 1 that is dissolved in the N-BUTYL ACETATE subsequently under uniform temp, 4-butyleneglycol-two (2 bromo 2 methyl propionic acid ester) (BDBIB).Polymerization time t at 3 hours
1Afterwards, extraction is used for determining molecular-weight average M
nThe sample of (by means of SEC) also adds monomer V2a (accurately the explanation of title and consumption is in table 3).This mixture of polymerization interrupts reaction until at least 98% transformation efficiency of expection and by being exposed to atmospheric oxygen and randomly adding methylene dichloride.By through the filtration of silica gel and remove volatile component this solution of purifying by distillation subsequently.Measure by SEC-at last and determine molecular-weight average.
Embodiment 7 (comparative example 2)
Be similar to embodiment 6, use monomer V1b and V2b (accurately the explanation of title and consumption is in table 3).
Embodiment 8 (comparative example 3)
Be similar to embodiment 6, use monomer V1c and V2c (accurately the explanation of title and consumption is in table 3).
Embodiment 9 (comparative example 4)
Be similar to embodiment 6, use monomer V1d and V2d (accurately the explanation of title and consumption is in table 3).
Table 3
| Embodiment | 6 | 7 | 8 | 9 |
| Monomer V1 | V1a)MMA | V1b)n-BA | V1c)n-BA | V1d)MMA |
| Consumption | 84.88g | 88.15g | 84.47g | 74.45g |
| Monomer V2 | V2a)MMA | V2b)MMA | V2c)n-BA | V2d)n-BA |
| Consumption | 15.12g | 11.85g | 15.13g | 25.55g |
| Initiator amount | 3.09g | 2.51g | 2.41g | 2.72g |
| M n(fs) | 7600 | - | 12900 | 9200 |
| M n(end product) | 8100 | 14500 | 13800 | 8400 |
| D | 1.25 | 1.29 | 1.26 | 1.23 |
The MMA=methyl methacrylate; The n-BA=n-butyl acrylate
Claims (28)
1. consist of in ABA and each the A block and have≤segmented copolymer of 4 functional groups, it is characterized in that,
Block A is the monomeric multipolymer that contains amine-functionalized (methyl) acrylate and be selected from (methyl) acrylate or its mixture,
B block contains (methyl) acrylate or its mixture with extra functional group,
Block A and B block polymerization are become ABA block copolymerization product.
2. segmented copolymer as claimed in claim 1 is characterized in that, amine-functionalized (methyl) acrylate is formula H
2C=CR
1-C (=O) XR
2NR
3R
4Monomer, wherein,
R
1Be hydrogen or methyl group and
R
2Expression straight chain, branch or the functionalized hydrocarbon fragment of alicyclic two-fold with 2 to 36 C atoms, its esterification by amino alcohol and acrylic or methacrylic acid is introduced,
X be oxygen or-NH-and
R
3And R
4Can be identical or different organic residue, described organic residue be selected from straight chain, branch or alicyclic alkyl residue and/or the aromatic yl residue with 2 to 20 C atoms.
3. segmented copolymer as claimed in claim 1 is characterized in that, described segmented copolymer contains polymerisable and do not belong to the monomer of (methyl) esters of acrylic acid by means of ATRP in block A and/or B block.
4. segmented copolymer as claimed in claim 1 is characterized in that, described segmented copolymer contains polymerisable and do not belong to the monomer of (methyl) esters of acrylic acid by means of ATRP in block A and/or B block with the amount of 0-50 weight %.
5. segmented copolymer as claimed in claim 1 is characterized in that, each A block of ABA segmented copolymer has and contains≤composition of 2 amine functional groups.
6. segmented copolymer as claimed in claim 1 is characterized in that, each A block account for ABA segmented copolymer gross weight less than 20%.
7. segmented copolymer as claimed in claim 6 is characterized in that, each A block account for ABA segmented copolymer gross weight less than 10%.
8. segmented copolymer as claimed in claim 1 is characterized in that, each A block itself can have AC diblock structure again and therefore cause ACBCA five segmented copolymers.
9. segmented copolymer as claimed in claim 8 is characterized in that, the composition of C block corresponding in the A block without the composition of amine-functionalized part.
10. segmented copolymer as claimed in claim 1, it is characterized in that, described amine-functionalized (methyl) acrylate is preferably from 2-dimethyl aminoethyl-methacrylic ester, 2-diethylamino ethyl-methacrylic ester, 2-tertiary butyl amino-ethyl-methacrylic ester, 2-dimethyl aminoethyl-acrylate, 2-diethylamino ethyl-acrylate, 2-tertiary butyl amino-ethyl-acrylate, 3-dimethylaminopropyl-Methacrylamide and 3-dimethylaminopropyl-acrylamide.
11. segmented copolymer as claimed in claim 1, it is characterized in that, described (methyl) acrylate is preferably from the straight chain with 1 to 40 C atom, (methyl) alkyl acrylate of branch or alicyclic alcohol, (methyl) methyl acrylate for example, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) vinylformic acid octadecane alcohol ester, (methyl) lauryl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid aryl ester is as (methyl) vinylformic acid benzyl ester or (methyl) phenyl acrylate, and they can have and are unsubstituted or 1-4 refetches the aromatic yl residue in generation; Ether with 5-80 C atom, polyoxyethylene glycol, the list of polypropylene glycol or their mixture (methyl) acrylate, for example tetrahydrofurfuryl methacrylic ester, methacrylic acid methoxy Ji Jia (second) oxygen base ethyl ester, methacrylic acid 1-butoxy propyl ester, methacrylic acid cyclohexyloxy methyl esters, methacrylic acid benzyloxy methyl esters, methacrylic acid chaff ester, methacrylic acid 2-butoxy ethyl ester, methacrylic acid 2-ethoxy ethyl ester, methacrylic acid allyloxy methyl esters, methacrylic acid 1-oxyethyl group butyl ester, methacrylic acid 1-ethoxy ethyl ester, methacrylic acid oxyethyl group methyl esters, poly-(ethylene glycol) methyl ether (methyl) acrylate or poly-(propylene glycol) methyl ether (methyl) acrylate.
12. segmented copolymer as claimed in claim 1 is characterized in that, described block A and/or B can contain vinyl ester, vinyl ether, fumarate, maleic acid ester, vinylbenzene, vinyl cyanide or other are by the polymerisable monomer of ATRP.
13. preparation consists of ABA and have in each A block≤method of the segmented copolymer of 4 amine groups, it is characterized in that, block A is the monomeric multipolymer that contains amine-functionalized (methyl) acrylate and be selected from (methyl) acrylate or its mixture, B block contains (methyl) acrylate or its mixture with amine functional group, is making block A and B block in the presence of initiator and the catalyzer and in the solvent of Halogen by means of atom transition free radical polymerization reaction (ATRP).
14. the method for preparing segmented copolymer as claimed in claim 13 is characterized in that, described initiator is dual functional initiator.
15. the method for preparing segmented copolymer as claimed in claim 14, it is characterized in that, preferably use 1 as dual functional initiator, 4-butyleneglycol-two-(2 bromo 2 methyl propionic acid ester), 1,2-ethylene glycol-two-(2 bromo 2 methyl propionic acid ester), 2,5-two bromo-diethylene adipates or 2,3-two bromo-ethyl maleates.
16. the method for preparing segmented copolymer as claimed in claim 13 is characterized in that, the segmented copolymer of described composition ABA makes by means of the sequential polymerization process.
17. the method for preparing segmented copolymer as claimed in claim 13 is characterized in that, uses transistion metal compound as catalyzer.
18. the method for preparing segmented copolymer as claimed in claim 17 is characterized in that, uses copper, iron, rhodium, platinum, ruthenium or nickel compound as catalyzer.
19. the method for preparing segmented copolymer as claimed in claim 18 is characterized in that, uses copper compound as catalyzer.
20. the method for preparing segmented copolymer as claimed in claim 13, it is characterized in that, before polyreaction, make catalyzer and nitrogenous, oxygen, sulphur or phosphorus and can generate one or more coordinate bonds with transition metal and converge with the compound that forms the metal ligand complex compound.
21. the method for preparing segmented copolymer as claimed in claim 20 is characterized in that, uses to contain the chelating ligand of N as ligand.
22. the method for preparing segmented copolymer as claimed in claim 21 is characterized in that, uses 2 as ligand, 2 '-two pyridines, N, N, N ', N ", N " five methyl diethylentriamine (PMDETA), three (2-amino-ethyl) amine (TREN), N, N, N ', N '-tetramethylethylened or 1,1,4,7,10,10-hexamethyl Triethylenetetramine (TETA).
23. the method for preparing segmented copolymer as claimed in claim 13 is characterized in that described segmented copolymer has the number-average molecular weight between 5000g/mol and 100000g/mol.
24. the method for preparing segmented copolymer as claimed in claim 23 is characterized in that described segmented copolymer preferably has the number-average molecular weight between the 7500g/mol to 25000g/mol.
25. the method for preparing segmented copolymer as claimed in claim 13 is characterized in that described segmented copolymer has the molecular weight distribution less than 1.8.
26. the method for preparing segmented copolymer as claimed in claim 25 is characterized in that, described segmented copolymer has preferably the molecular weight distribution less than 1.4.
27. consisting of ABA and in each A block, have≤segmented copolymer of 4 amine groups is used for the purposes of jointing material, sealing material, reactive hot-melt adhesive, it is characterized in that,
Block A is the monomeric multipolymer that contains amine-functionalized (methyl) acrylate and be selected from (methyl) acrylate or its mixture,
B block contains (methyl) acrylate or its mixture with amine functional group, will
Block A and B block polymerization become ABA block copolymerization product.
28. consisting of ABA and in each A block, have≤segmented copolymer of 4 amine groups is as the purposes of the binding agent in the paint vehicle preparaton, reactive component or dispersion agent, it is characterized in that,
Block A is the monomeric multipolymer that contains amine-functionalized (methyl) acrylate and be selected from (methyl) acrylate or its mixture,
B block contains (methyl) acrylate or its mixture with amine functional group, will
Block A and B block polymerization become the ABA segmented copolymer.
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|---|---|---|---|
| DE102006035726.4 | 2006-07-28 | ||
| DE102006035726A DE102006035726A1 (en) | 2006-07-28 | 2006-07-28 | Process for the preparation of (meth) acrylate-based ABA triblock copolymers |
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| CN101466751A true CN101466751A (en) | 2009-06-24 |
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ID=38197685
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|---|---|---|---|
| CNA2007800215105A Pending CN101466751A (en) | 2006-07-28 | 2007-04-12 | Method for the production of (meth)acrylate-based ABA triblock copolymers |
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| Country | Link |
|---|---|
| US (1) | US8106129B2 (en) |
| EP (1) | EP2046849B1 (en) |
| JP (1) | JP2009544830A (en) |
| KR (1) | KR20090046804A (en) |
| CN (1) | CN101466751A (en) |
| AT (1) | ATE469930T1 (en) |
| BR (1) | BRPI0714980A2 (en) |
| CA (1) | CA2659287A1 (en) |
| DE (2) | DE102006035726A1 (en) |
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| WO (1) | WO2008012116A1 (en) |
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| JP2013087232A (en) * | 2011-10-20 | 2013-05-13 | Nippon Soda Co Ltd | Novel copolymer |
| JP6157837B2 (en) * | 2012-11-06 | 2017-07-05 | キヤノンファインテック株式会社 | ABXBA type block copolymer |
| RU2537002C1 (en) * | 2013-12-26 | 2014-12-27 | Федеральное Государственное Бюджетное Образовательное Учреждение Высшего Профессионального Образования "Нижегородский Государственный Университет Им. Н.И. Лобачевского" | Method of obtaining triblockcopolymers of methacrylic monomers |
| FI126972B (en) | 2014-04-11 | 2017-08-31 | Kemira Oyj | Water-soluble cross-linked block copolymers |
| US9587062B2 (en) | 2014-12-15 | 2017-03-07 | Henkel IP & Holding GmbH and Henkel AG & Co. KGaA | Photocrosslinkable block copolymers for hot-melt adhesives |
Family Cites Families (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0265254A3 (en) * | 1986-10-23 | 1990-03-21 | E.I. Du Pont De Nemours And Company | Oil additives |
| CA2153009C (en) * | 1994-07-07 | 2007-05-08 | Gary D. Grabaum | Constant velocity joint boot and method of making the same |
| DE19539214A1 (en) * | 1995-10-21 | 1997-04-24 | Degussa | Fire-safe, transparent pane element and its use |
| US6498209B1 (en) * | 1998-03-31 | 2002-12-24 | Roehm Gmbh & Co. Kg | Poly(meth)acrylate plastisols |
| WO2000041738A1 (en) * | 1999-01-12 | 2000-07-20 | Quanam Medical Corporation | Polymer compositions for intraluminal stent |
| US6306994B1 (en) * | 1999-05-14 | 2001-10-23 | E. I. Du Pont De Nemours And Company | Inks with enhanced substrate binding characteristics |
| US6288173B1 (en) * | 1999-06-03 | 2001-09-11 | Ppg Industries Ohio, Inc. | Block copolymers |
| DE19928352A1 (en) * | 1999-06-21 | 2000-12-28 | Roehm Gmbh | Plastisol use for mould articles, comprises (meth)acrylate (co)polymer(s) with bimodal or multi-modal prim. particle distribution prepared from methyl methacrylate, (meth) acrylate, vinyl monomer and adhesion aiding monomers |
| CN1240796C (en) | 2000-05-19 | 2006-02-08 | 阿克佐诺贝尔股份有限公司 | Aqueous cross-likable binder composition and coating, lacquer or sealing composition comprising such binder composition |
| US6767968B1 (en) * | 2000-10-03 | 2004-07-27 | Symyx Technologies, Inc. | ABA-type block copolymers having a random block of hydrophobic and hydrophilic monomers and methods of making same |
| WO2002028358A1 (en) * | 2000-10-03 | 2002-04-11 | Unilever Plc | Cosmetic and personal care compositions |
| DE10065501A1 (en) * | 2000-12-28 | 2002-07-04 | Roehm Gmbh | Process for the preparation of bead polymers with an average particle size in the range from 1 to 40 μm and molding compounds, beads and PAMA plastisols containing bead polymer |
| AU2002258649A1 (en) * | 2001-03-30 | 2002-10-28 | Rhodia Inc. | Aqeuous suspension of nanoparticles comprising an agrochemical active ingredient |
| JP2003064139A (en) * | 2001-08-24 | 2003-03-05 | Dainippon Toryo Co Ltd | Pigment-dispersing resin and coloring paint composition containing the same resin |
| TW200407363A (en) * | 2001-11-29 | 2004-05-16 | Ciba Sc Holding Ag | Pigment compositions with modified ATRP copolymer dispersants |
| US20050106117A1 (en) * | 2002-03-12 | 2005-05-19 | Gerald Adams | Triblock copolymers for cosmetic or personal care compositions |
| FR2840546B1 (en) * | 2002-06-07 | 2005-02-25 | Atofina | METHOD FOR MIXING CONTENT DYNAMICALLY AT LEAST TWO FLUIDS AND MICROMELANGER |
| DE10227898A1 (en) * | 2002-06-21 | 2004-01-15 | Röhm GmbH & Co. KG | Process for the preparation of spray-dried poly (meth) acrylate polymers, their use as polymer component for plastisols and plastisols prepared therewith |
| JP2006505686A (en) * | 2002-11-07 | 2006-02-16 | ロディア・シミ | Copolymers of controlled structure containing amphoteric or zwitterionic moieties |
| US20050080176A1 (en) * | 2003-10-08 | 2005-04-14 | Robb Ian D. | Crosslinked polymer gels for filter cake formation |
| JP2005126483A (en) * | 2003-10-21 | 2005-05-19 | Mitsubishi Chemicals Corp | (meth)acrylic-modified polyolefin resin, its manufacturing process and composition |
| DE10350786A1 (en) * | 2003-10-29 | 2005-06-02 | Röhm GmbH & Co. KG | Mixtures for the production of reactive hot melt adhesives and reactive hot melt adhesives obtainable therefrom |
| DE10359973A1 (en) * | 2003-12-18 | 2005-07-21 | Tesa Ag | Adhesive material for use on adhesive tape, comprises an acrylate block copolymer comprising (co)polymer blocks with low softening points, which exist in microphase-separated domains under usage conditions |
| DE102004001412A1 (en) * | 2004-01-09 | 2005-08-25 | Tesa Ag | Pressure-sensitive adhesive based on an acrylate polymer blend |
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| DE102004035937A1 (en) * | 2004-07-23 | 2006-02-16 | Röhm GmbH & Co. KG | Plastisols with reduced water absorption |
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-
2006
- 2006-07-28 DE DE102006035726A patent/DE102006035726A1/en not_active Withdrawn
-
2007
- 2007-04-12 CA CA002659287A patent/CA2659287A1/en not_active Abandoned
- 2007-04-12 MX MX2009000598A patent/MX2009000598A/en unknown
- 2007-04-12 RU RU2009106951/04A patent/RU2009106951A/en not_active Application Discontinuation
- 2007-04-12 DE DE502007004026T patent/DE502007004026D1/en active Active
- 2007-04-12 WO PCT/EP2007/053533 patent/WO2008012116A1/en active Application Filing
- 2007-04-12 KR KR1020097001683A patent/KR20090046804A/en not_active Application Discontinuation
- 2007-04-12 JP JP2009522189A patent/JP2009544830A/en active Pending
- 2007-04-12 US US12/301,903 patent/US8106129B2/en not_active Expired - Fee Related
- 2007-04-12 CN CNA2007800215105A patent/CN101466751A/en active Pending
- 2007-04-12 EP EP07728001A patent/EP2046849B1/en not_active Not-in-force
- 2007-04-12 BR BRPI0714980-8A patent/BRPI0714980A2/en not_active IP Right Cessation
- 2007-04-12 AT AT07728001T patent/ATE469930T1/en active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106800627A (en) * | 2010-05-19 | 2017-06-06 | 艾利丹尼森公司 | Organized architecture in acrylic polymer |
| CN106800627B (en) * | 2010-05-19 | 2020-08-07 | 艾利丹尼森公司 | Ordered architecture in acrylic polymers |
| CN103374107B (en) * | 2012-04-26 | 2015-09-16 | 株式会社理光 | ABA triblock copolymer, thickening material and aqueous composition |
| CN103374107A (en) * | 2012-04-26 | 2013-10-30 | 株式会社理光 | Aba triblock copolymer, thickener, and aqueous compositon |
| CN105121487A (en) * | 2013-05-02 | 2015-12-02 | 株式会社Lg化学 | Multi-block copolymer |
| CN105121487B (en) * | 2013-05-02 | 2017-12-19 | 株式会社Lg化学 | Segmented copolymer |
| US10308751B2 (en) | 2013-08-30 | 2019-06-04 | Lg Chem, Ltd. | Block copolymer |
| CN105593256A (en) * | 2013-08-30 | 2016-05-18 | 株式会社Lg化学 | Block copolymer |
| CN108079980A (en) * | 2016-11-21 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of chromatographic column and preparation and application with hydrophobicity brush-type polymer coating |
| CN110546175A (en) * | 2017-04-21 | 2019-12-06 | 汉高股份有限及两合公司 | (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymers, method for the production thereof and use thereof |
| CN110546175B (en) * | 2017-04-21 | 2022-01-04 | 汉高股份有限及两合公司 | Functionalized poly (meth) acrylate-polyimide-poly (meth) acrylate block copolymers, methods and uses thereof |
| CN108417836A (en) * | 2018-01-31 | 2018-08-17 | 闽南师范大学 | A kind of binders for electrodes of new type lithium ion battery and preparation method thereof |
| CN114258348A (en) * | 2019-09-03 | 2022-03-29 | 凸版印刷株式会社 | Coating agent for modifying heat-seal substrate, laminate, and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102006035726A1 (en) | 2008-01-31 |
| CA2659287A1 (en) | 2008-01-31 |
| BRPI0714980A2 (en) | 2012-12-25 |
| KR20090046804A (en) | 2009-05-11 |
| RU2009106951A (en) | 2010-09-10 |
| MX2009000598A (en) | 2009-01-28 |
| EP2046849B1 (en) | 2010-06-02 |
| JP2009544830A (en) | 2009-12-17 |
| US20100280182A1 (en) | 2010-11-04 |
| ATE469930T1 (en) | 2010-06-15 |
| WO2008012116A1 (en) | 2008-01-31 |
| DE502007004026D1 (en) | 2010-07-15 |
| US8106129B2 (en) | 2012-01-31 |
| EP2046849A1 (en) | 2009-04-15 |
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Application publication date: 20090624 |